1-(benzamido)pyridinium salts

ABSTRACT

Compounds of formula   IN WHICH R1, R2, R3, R4 and R5 are the same or different and each represents hydrogen, halogen, nitro, alkyl, substituted alkyl, alkoxy, carboxy or an ester, amide or mono- or di-substituted amide thereof, aryl, heterocyclic, aralkyl, cyano or hydroxy, with the proviso that R3 does not represent a second group of formula I or II in which R3 is merely a bond; R6 represents a group of formula COR8, COOR8, CONR8R9 or SO2R8, in which R8 represents alkyl, substituted alkyl, aryl, substituted aryl, aralkyl, substituted aralkyl, aralkenyl, substituted aralkenyl, cycloalkyl or heterocyclic, and R9 represents hydrogen, alkyl, substituted alkyl, phenyl or substituted phenyl; R7 represents hydrogen, alkyl of 1 to 4 carbon atoms or a group as defined under R6; and X represents one equivalent of an anion are acaricides, especially for use on crops.

United States Patent Parsons [4 1 May 27, 1975 1-( BENZAMIDO )PYRIDINIUM SALTS [75] Inventor: John Henry Parsons, Saffron Walden, England [73] Assignee: Fisons Limited, London, England [22] Filed: Jan. 5, 1973 [21] Appl. No.: 321,476

[30] Foreign Application Priority Data Jan. 5, 1972 United Kingdom 369/72 [52] U.S. Cl.. 260/295 Q; 260/240 D; 260/294.8 D; 260/294.8 C; 260/295 K; 260/295.5 A; 260/247.2 A; 424/263; 424/266; 424/248 [51] Int. Cl C07d 31/44 [58] Field of Search 260/295 Q [56] References Cited OTHER PUBLICATIONS Potts et al., J. Org. Chem., Vol. 33, (10), Pages 37664770, October 1968.

Primary Examiner-Alan L. Rotman Attorney, Agent, or Firm-Wenderoth, Lind & Ponack [5 7] ABSTRACT Compounds of formula in which R, R R R and R are the same or different and each represents hydrogen, halogen, nitro, alkyl, substituted alkyl, alkoxy, carboxy or an ester, amide or monoor di-substituted amide thereof, aryl, heterocyclic, aralkyl, cyano or hydroxy, with the proviso that R does not represent a second group of formula I or II in which R is merely a bond;

19 Claims, No Drawings 1 1- (BENZAMIDO)PYRIDINIUM SALTS This invention relates to acaricides.

A new group of acaricides has been discovered, which has very valuable properties. The compounds are of low mammalian toxicity. Moreover they are of low herbicidal and insecticidal activity and hence can be used to combat acarids on desired plants without harming the plants and to combat acarids without harming beneficial insects such as bees. Furthermore, besides having direct contact action against acarids, many of the compounds are systemic within plants and hence can be used on plants even though not all the affected parts of the plant are contacted during application and even by application to the soil in which the plants are growing or are to grow.

Accordingly, the invention includes a method of combating acarids at a locus infested or liable to be infested with them, which method comprises applying to the locus an acarid-combating amount of a compound of general formula in which R R R, R and R are the same of different and each represents hydrogen, halogen (for example chloro or bromo), nitro, alkyl (for example of 1 to 4 carbon atoms such as methyl, ethyl or isopropyl), substituted alkyl (for example the alkyl group substituted by hydroxy or halogen, such as hydroxymethyl, chloromethyl or trifluoromethyl), alkoxy (for example of l to 4 carbon atoms such as methoxy, ethoxy or isopropoxy), carboxy or an ester (for example with an alkanol of l to 4 carbon atoms), amide or monoor disubstituted amide (for example substituted by alkyl of 1 to 4 carbon atoms) thereof, aryl (for example phenyl), heterocyclic (for example furyl, morpholino or a second group of formula I or II in which one of R R R, R and R is merely a bond), aralkyl (for example whose alkyl group contains 1 to 4 carbon atoms, such as benzyl or phenethyl), cyano or hydroxy; R represents a group of formula COR, COOR, CONRR r SO R in which R represents alkyl (for example of l to 8 preferably 1 to 4 carbon atoms such as methyl, ethyl or isopropyl), substituted alkyl (for example the alkyl group substituted by halogen, alkoxycarbonyl of 2 to carbon atoms, alkoxy, e.g. of l to 4 carbon atoms, or by phenoxy substituted by halogen and/or alkyl of l to 4 carbon atoms, such as trifluoromethyl, chloroethyl, ethoxyethyl or 2-methyl-4- chlorophenoxymethyl), aryl (for example phenyl), substituted aryl (for example the aryl group substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, acetamido, nitro and alkoxy of l to 4 carbon atoms, such as chlorophenyl, dichlorophenyl, tolyl, xylyl, fluorophenyl, nitrophenyl, methoxyphenyl or 3-methyl-4-chlorophenyl), aralkyl (for example whose alkyl group contains 1 to 4 carbon atoms, such as benzyl), substituted aralkyl (for example the aralkyl group substituted by halogen, such as chlorobenzyl),

aralkenyl (for example styryl), substituted aralkenyl (for example the aralkenyl group substituted by halogen, such as chlorostyryl), cycloalkyl (for example of 3 to 8 carbon atoms, such as cyclohexyl) or heterocy clic (for example furyl, thienyl, benzofuryl or pyridyl), and R represents hydrogen, alkyl (for example of 1 to 8 preferably 1 to 4 carbon atoms such as methyl, ethyl or isopropyl), substituted alkyl (for example the alkyl group substituted by halogen or alkoxy, e.g. of l to 4 carbon atoms, such as trifluoromethyl, chloroethyl or ethoxyethyl), phenyl or substituted phenyl (for example substituted by halogen or alkyl of l to 4 carbon atoms, such as chlorophenyl, dichlorophenyl, tolyl or xylyl); R represents hydrogen, alkyl of l to 4 carbon atoms or a group as defined under R; and X represents one equivalent of an acaracidally effective anion (for example Cl, Br, I, CH SO NO or /2 S0 with the proviso that R is not a second group offormula I or II in which R is merely a bond. The substituents defined above include acidic and basic groups and where salt formation can take place as a result at such groups, the compounds may be present as such salts. For example, l-nicotinamido-S-methylpyridinium chloride may be in the form of its hydrochloride, 1- nicotinamido-3-methylpyridinium chloride hydrochloride.

In addition, the invention includes as new com pounds the present compounds except those in which R represents acetyl, propionyl, trifluoroacetyl, benzoyl, methoxycarbonyl, ethoxycarbonyl, ptolylsulphonyl, sulphanilyl or N-acetylsulphanilyl.

The invention also provides acaricidal compositions containing the present compounds, particularly a composition comprising such a compound together with a surface active agent; a solid composition comprising such a compound together with a solid carrier; a liquid composition comprising such a compound together with a hydrocarbon of boiling point in the range l30-270C; and a composition comprising such a compound together with another agrochemical pesticide especially another acaricide.

The compounds of formula I may be prepared be reacting a l-amino-pyridinium salt of formula I N 11 \II (III) with a halide or anhydride of formula R Y or ROR respectively (in which Y represents halogen). The reaction may be carried out in an organic solvent in which the desired product is insoluble, for example a hydrocarbon such as xylene. Alternatively the reaction may be carried out without a solvent, using excess of the compound R Y or R OR.

Alternatively, compounds of formula I may be prepared by reacting a compound of formula II with a compound of formula RX. When R represents hydrogen, an external salt of formula I corresponding to the internal salt of formula II is simply prepared; but when R represents other than hydrogen (e.g. when the compound of formula RX is dimethyl sulphate or pchlorobenzoyl chloride), an external salt of formula I which has no counterpart of formula II is prepared.

The compounds of formula Il may be prepared by treating those of formula I wherein R represents hydrogen with a bsse, such as sodium hydroxide.

It can be seen that the compounds of formula II are the corresponding internal salts of the compounds of formula I wherein R represents hydrogen. Such compounds of the two types are equivalent. In aqueous solution of such compounds of formula I an equilibrium exists with the compounds of formula II, for example:

Such pairs of equivalent compounds are of similar activity in use. Since in the compounds of formula I it is the cation which is responsible for the acaricidal activity, any anion can generally be employed and it can thus be chosen bearing other factors in mind such as convenience in manufacture of the cation. X is suitably chloride.

In a particular embodiment of the present compounds R, R R, R and R are the same or different and each represents hydrogen, halogen, nitro, alkyl, substituted alkyl, alkoxy, carboxy or an ester, amide or monoor di-substituted amide thereof, aryl, aralkyl, cyano or hydroxy. New compounds within this group include the compounds in which R represents CONR R COR in which R represents substituted aryl, aralkyl, substituted aralkyl, aralkenyl, substituted aralkenyl, cycloalkyl or heterocyclic; COOR in which R represents substituted alkyl, aryl, substituted aryl, aralkly, substituted aralkyl, aralkenyl, substituted aralkenyl, cycloalkyl or heterocyclic; or 50 R in which R represents alkyl, substituted alkyl, aryl, aralkyl, substituted aralkyl, aralkenyl, substituted aralkenyl, cycloalkyl or heterocyclic.

In another particular embodiment, R, R R", R and R are the same or different and each represents hydrogen, halogen, nitro, alkyl, alkoxy, carboxy or an ester,

amide or monoor di-substituted amide thereof, aryl, aralkyl, or hydroxy;

R represents alkyl, substituted alkyl, phenyl or substituted phenyl; and

R represents hydrogen. Preferred amongst this group of compounds are those wherein R is phenyl optionally substituted, preferably monosubstituted, by chlorine. New compounds within the group include the compounds in which R represents CONR R COR in which R represents substituted phenyl; COOR in which R represents substituted alkyl, phenyl or substituted phenyl; or 50 R in which R represents alkyl, substituted alkyl or phenyl.

A more specific group of the present compounds are those wherein R R R, R and R are the same or different and each represents hydrogen, halogen, nitro, alkyl of l to 4 carbon atoms, alkyl or 1 to 4 carbon atoms substituted by hydroxy or halogen. alkoxy of 1 to 4 carbon atoms, carboxy, alkoxycarbonyl whose alkoxy group contains 1 to 4 carbon atoms, carbamoyl, N- alkylcarbamoyl whose alkyl group contains 1 to 4 carbon atoms,,N,N-dialkylcarbamoyl whose alkyl groups are the same or different and contain 1 to 4 carbon atoms, phenyl, furyl, morpholino, a second group of formula I or II in which one of R R R, R and R is merely a bond, phenylalkyl of 7 to 10 carbon atoms, cyano or hydroxy, with the proviso that R does not represent a second group of formula I or II in which R is merely a bond;

R represents alkyl of l to 8 carbon atoms; alkyl of l to 8 carbon atoms substituted by halogen, alkoxycarbonyl of 2 to 5 carbon atoms, alkoxy of l to 4 carbon atoms, or by phenoxy substituted by halogen and/or alkyl of l to 4 carbon atoms; phenyl; naphthyl; phenyl or naphthyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, nitro and alkoxy of l to 4 carbon atoms; phenylalkyl of 7 to 10 carbon atoms substituted by halogen; styryl; styryl substituted by halogen; cycloalkyl of 3 to 8 carbon atoms; furyl; thienyl; benzofuryl; or pyridyl; and R represents hydrogen; alkyl of l to 8 carbon atoms; alkyl of l to 8 carbon atoms substituted by halogen or alkoxy of l to 4 carbon atoms; phenyl; or phenyl substituted by halogen or alkyl of l to 4 carbon atoms.

For convenience in manufacture, the present compounds can be those wherein R, R R, R and R are the same or different and each represents hydrogen or alkyl of l to 4 carbon atoms;

R represents alkyl of l to 8 carbon atoms; alkyl of 1 to 8 carbon atoms substituted by alkoxycarbonyl of 2 to 5 carbon atoms or by phenoxy substituted by halogen and/or alkyl of l to 4 carbon atoms; phenyl; naphthyl; phenyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, nitro and alkoxy of 1 to 4 carbon atoms; phenylalkyl of 7 to 10 carbon atoms; phenylalkyl of 7 to 10 carbon atoms substituted by halogen; styryl; styryl substituted by halogen; cycloalkyl of 3 to 8 carbon atoms; fury]; thienyl; benzofuryl; or pyridyl;

R represents hydrogen or alkyl of l to 8 carbon atoms; and

R represents hydrogen, alkyl of l to 4 carbon atoms or benzoyl substituted by halogen. A preferred group of these compounds are these wherein R represents alkyl of l to 8 carbon atoms; alkyl of 1 to 8 carbon atoms substituted by phenoxy substituted by halogen; phenyl; phenyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, nitro and alkoxy of 1 to 4 carbon atoms; phenyalkyl of 7 to 10 carbon atoms; styryl; styryl substituted by halogen; cycloalkyl of 3 to 8 carbon atoms; benzofuryl; or pyridyl.

It is preferred that R represents hydrogen.

Usually at least three, and preferably at least four, of R R R R and R represent hydrogen.

Preferably at least one of R and R represents hydrogen.

The most preferred compounds are those wherein R represents COR or COOR especially where R represents phenyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, nitro and alkoxy of l to 4 carbon atoms. Such especially preferred compounds are not only highly active but are active over long periods, e.g. l-(pchlorobenzamido)pyridinium chloride can protect cucumbers for 2 months or more. Moreover, such especially preferred compounds are active against strains of mites which are resistant to standard acaricides, such as Dicofol, Chlorobenzilate, Tetradifon and Dimethoate.

A preferred group of new compounds are those of general formula I or II in which R, R R, R and R are the same or different and each represents hydrogen or alkyl or 1 to 4 carbon atoms;

R represents a group of formula COR", COOR, CONR R in which R represents phenyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, nitro and alkoxy of l to 4 carbon atoms; phenylalkyl of 7 to 10 carbon atoms; phenylalkyl of 7 to 10 carbon atoms substituted by halogen; styryl; styryl substituted by halogen; cycloalkyl of 3 to 8 carbon atoms; fury]; pyridyl; benzofuryl or thienyl; R represents phenyl; phenyl substituted by halogen and/or alkyl of 1 to 4 carbon atoms; or benzofuryl; R

represents alkyl of l to 8 carbon atoms; phenyl; phenyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms and alkoxy of l to 4 carbon atoms; and R represents hydrogen or alkyl of l to 8 carbon atoms;

R represents hydrogen, alkyl of l to 4 carbon atoms or benzoyl substituted by halogen; and

X represents one equivalent of an anion. Desirably within this group R represents phenyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, nitro and alkoxy of l to 4 carbon atoms; phenylalkyl of 7 to 10 carbon atoms; styryl; styryl substituted by halogen; cycloalkyl of 3 to 8 carbon atoms; or pyridyl; R represents phenyl; phenyl substituted by halogen and/or alkyl of l to 4 carbon atoms; or benzofuryl; and R represents alkyl of l to 8 carbon atoms or phenyl substituted by halogen.

Outstandingly active and most preferred are compounds of general formula I and II in which four of R R R, R and R represent hydrogen and the fifth represents hydrogen or alkyl of l to 4 carbon atoms; R represents benzoyl substituted by one or two substituents selected from halogen, alkyl of l to 4 carbon atoms and nitro; and X represents one equivalent of an anion. The most promising particular compounds within this group are:

l-(p-chlorobenzamido)pyridinium salts;

l-(p-chlorobenzamido)-2-methylpyridinium salts; l-(p-chlorobenzamido)-3-methylpyridinium salts; l-(p-chlorobenzamido)-4-methylpyridinium salts;

l-( 3,4-dichlorobenzamido)pyridinium salts; and

l-(4-nitrobenzamido)pyridinium salts; especially the first-mentioned and especially the internal salts of these compounds and the chlorides of the first five.

The present compounds are usually employed in the form of compositions containing the active ingredients. Usually compositions are initially produced in the form of concentrates, e.g. containing 20-98 active ingredient, and these are diluted with water for application,

e.g. so that the concentration of active ingredient is 0.0l0.5 Parts and percentages in this specification are by weight unless otherwise indicated.

The compositions normally contain a carrier and/or a surface active agent.

The carrier may be a liquid, e.g. water (e.g. water used to dilute a concentrate for application). Many of the compounds are water soluble crystalline solids and can be used in the form of aqueous solutions. If water is employed as carrier in a concentrate, an organic solvent may also be present as carrier, though this is not usually employed. A surface active agent may advantageously be present.

The carrier may be a liquid other than water, for example an organic solvent, usually a water-immiscible solvent, e.g. a hydrocarbon which boils within the range l30-270C, in which the compounds are dissolved or suspended. A concentrate containing an organic solvent suitably also contains a surface active agent so that the concentrate acts as a self-emulsifiable oil on admixture with water.

The carrier may be a solid, which may be finely divided. Examples of suitable solids are clays, sand, mica, chalk, attapulgite, diatomite, perlite and sepiolite, and synthetic solid carriers, e.g. silicas, silicates and lignosulphonates.

Wettable powders soluble or dispersible in water may be formed by admixing the compounds with or without a carrier with a surface active agent.

Aqueous solutions and Wettable powders are the preferred concentrates since the compounds are of comparatively low solubility in organic solvent such as hydrocarbons. A compound of formula I where R represents hydrogen tends to be more soluble in water but less soluble in organic solvents such as hydrocarbons than the corresponding compound of formula II. Thus, in making up an emulsifiable concentrate in a hydrocarbon the compound in the form of an internal salt of formula II would generally be favoured, while in making up an aqueous solution the compound in the form of an external salt of formula I would generally be favoured.

The term surface active agent is used in the broad sense to include materials variously called emulsifying agents, dispersing agents and wetting agents. Such agents are well known in the art.

The surface active agents used may comprise anionic surface active agents, for example soaps, fatty sulphate esters such as dodecyl sodium sulphate, octadecyl sodium sulphate and cetyl sodium sulphate, fatty aromatic sulphonates such as alkyl-benzene sulphonates or butyl-naphthalene sulphonates, more complex fatty sulphonates such as the amide condensation product of oleic acid and N-methyl taurine or the sodium sulphonate of dioctyl succinate.

The surface active agents may also comprise nonionic agents, for example condensation products of fatty acids, fatty alcohols or fatty substituted phenols with ethylene oxide, or fatty esters and ethers of sugars or polyhydric alcohols, or the products obtained from the latter by condensation with ethylene oxide, or the products known as block copolymers of ethylene oxide and propylene oxide.

The surface active agents may also comprise cationic agents, for example cetyl trimethylammonium bromide.

Preferred surface active agents are non-ionic surface active agents.

The present compounds are useful as acaricides. They are particularly active against the eggs of mites, preventing the eggs from hatching, and are also active against the larval and nymphal stages. Furthermore, when adult female mites are treated with a non-toxic dosage of the compound, the mites eggs fail to hatch.

The present active compounds may be admixed with other agrochemical pesticides, for example herbicides, insecticides, fungicides or other acaricides, or fertilizers. Examples of pesticides with which the compounds may be mixed are Dicofol (2,2,2-trichloro-1,1-di(4- chlorophenyl)ethanol), Fenazaflor ,6-dichloro-1- phenoxycarbonyl-2-trifluoromethylbenzimidazole),

tricyclohexyltin hydroxide, Tetradifon (2,4,4',5- tetrachlorodiphenyl), sulphone), Formetanate (3- dimethylaminomethyleneiminophenyl N- methylcarbamate), Chlorodimeform (N,N-dimethyl- N-(2-methyl-4-chlorophenyl)formamidine), Chlorobenzilate (ethyl 4,4'-dichlorobenzilate), Quinomethionate (6-methyl-2-oxo-l ,3-dithiolo[4,5- b]quinoxaline), Endosulfan (6,7,89,10,10- hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano- 2,4,3-benzodioxathiepin 3-oxide), Chlorodecone (decachloro-octahydro-l ,3 ,4-metheno- 21-1,SH,cyclobuta[cd]pentalen-2-one), bis(pentachloro-2,4-cyclopentadien-l-yl), Chloropropylate (isopropyl 4,4'-dichlorobenzilate), Bromopropylate (isopropyl 4,4'-dibromobenzilate), Thioquinox (2thio-1,3- dithiolo-[4,5-b]quinoxaline), Dinocap (dinitrooctylphenyl crotonate), Binapacryl (2-sec-butyl-4,6- dinitrophenyl 2-methylcrotonate), Dinobuton (2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate), Naled (l,2-dibromo-2,2-dichloroethyl dimethyl phosphate), Monocrotophos (dimethyl 1methyl-2- methylcarbamoyl)-vinyl phosphate), Demeton (diethyl 2-(ethy1thio) ethylthiophosphate), Phorate (0,0- diethyl S-(ethylthiomethyl) phosphorodithioate), Oxydemeton-methyl (0,0-dimethyl S-(2,ethylsulphinylethyl)phosphorothioate), Ethion (tetraethyl S,S-methylenebis(phosphorodithioate)), Formothion (S-(N-formyl-N-methylcarbamoylmethyl) dimethyl phosphorodithioate, Ethoate-methyl (S-(N-ethylcarbamoylmethyl) dimethyl phosphorodithioate), Di-

methoate (dimethyl S-(N-methylcarbanoylmethyl) phosphorodithioate), Cyanthoate (S-(hl-(lcyano-lmethylethyl)carbamoylmethyl) diethyl phosphorothio ate), EPN (O-ethyl O-p-nitrophenyl phenylphosphonothioate), Carbophenothion (S-(4-chloropheny1thiomethyl) diethyl phosphorodithioate), Methidathion (S-(2,3-dihydro-5-methoxy-2oxo-1,3 ,4-thiadiazol-3- ylmethyl) dimethyl phosphorodithioate), Chloropyrifos (diethyl 3,5,6-trichloro-2-pyridyl phosphorothionate), Diazinon (diethyl 2-isopropyl-6- methyl-4pyrimidinyl phosphorothionate), Azinphosethyl (diethyl S-(4-oxo-1,2,3-benzotriazin-3-ylmethyl) phosphorodithioate), Azinphos-methyl (dimethyl S-(4- oxo-l ,2,3-benzotriazin-3-ylmethyl phosphorodithioate), Fenson (4-chlorophenyl benzenesulphonate), Tetrasul (2,4,4,5-tetrachlorodiphenyl sulphide), Chlorobenside (4chlorobenzy1 4-chlorophenyl sulphide), Chlorfensulphide (4-chlorophenyl 2,4,5- trichlorophenylazo sulphide) 2-(p-tert-butylphenoxy)- lmethylethyl 2chloroethyl sulphite, 2(p-tert- 8 butylphenoxy)cyclohexyl 2-propynyl sulphite, Aldicarb (Z-methyl-Z-(methylthio)propionaldehyde 0-(methylcarbamoyl)oxime), Methomyl (S-methyl-N- methylcarbamoyloxy) thioacetimidate), Methiocarb (4-methylthio3,5-xylyl N-methylcarbamate), and Benomyl (methyl l-(butycarbamoyl)benzimidazole-2- carbamate).

Particularly useful are mixtures with other acaricides which have rapid knockdown to adult mites. These mixtures combine activity against adult mites and ovicidal activity against the following generation. A particularly suitable such acaricide is Dicofol.

Mixtures with insecticides are useful in broadening the spectrum of pest species against which the compositions are effective.

Mixtures with fungicides can combine protection against mites with protection against fungi. Particularly useful are mixtures with fungicides controlling scab and mildew diseases, such as Benomyl, Dinocap and Quinomethionate.

The present compositions may be formed by admixing the ingredients.

The compounds may be applied to stored products, animals, the land, the soil or plants. The compounds are of interest particularly to combat mites which infest or are liable to infest desired plants especially crops and particularly food crops. Preferably, the compounds are applied to crops or to soil in which crops are growing or are immediately after application to grow. The compounds are safe to a wide variety of crops and can be used against mites in the field or in the greenhouse. Examples of crops on which the compounds can be used are apples, pears, strawberries, plums, citrus, vines, cotton, ornamentals, cucumbers and tomatoes. When applied to land, the soil or plants, the compounds may generally be used at a rate within the range 0.1-4, preferably 0.1-2, kg per hectare. They are active against various mite species for example the greenhouse red spider mite, Tetranychus telarius and hop red spited mite Tetranchus urticae.

The invention is illustrated by the following Examples.

EXAMPLE 1 1-Aminopyridinium chloride (104 parts) and pchlorobenzoyl chloride (150 parts) were heated in xylene (750 parts) at C for 4 hours. The solid prodact was fi tered off and recrystallized from n-butanol to give 1-(p-chlorobenzamido)pyridinium chloride (209 parts, 97% yield), melting point 241C.

Analysis:

Found: C. 53.

H, 3.85; N, 10.60%. H, 3

EXAMPLE 2 Found. C, 53.70; H, N, 14.15%, C,,H ClN- ,O requires: C. 53.87; H, N, 13.96%.

EXAMPLES 3-95 The following were prepared by analogous methods to those of Examples 1 and 2:

l-Acetamidopyridinium chloride l-( Ethoxycarbonylamino)pyridinium chloride lNonanamidopyridinium chloride l-Benzamidopyridinium chloride l-(p-Fluorobenzamido)pyridinium chloride l(p-Toluamido)pyridinium chloride l-(2,4-Dichlorobenzamido)pyridinium chloride l-(pNitrobenzamido)pyridinium chloride l(m-Nitrobenzamido)pyridinium chloride l-(p-Chlorobenzamido)-2-methylpyridinium chloride l-(p-toluamido)-2-methylpyridinium chloride l-( 3,4-dichlorobenzamido)pyridinium chloride l-benzamido-2-methylpyridinium chloride l-(3,4dichlorobenzamido)-2-methylpyridinium chloride l-(o-chlorobenmmido)pyridinium chloride l(panisamido)pyridinium chloride -(p-nitrobenzarnido)Q-methylpyridiniurn chloride -(o-iodobenzamido)pyridinium chloride -(p-chlorobenzamido-4-methylpyridinium chloride -(o-toluamido)pyridinium chloride -(o-toluamido)-4-methylpyridinium chloride -(p-tert-butylbenzamidopyridinium chloride -(p-tertbutylbenzamido )-4-methylpyridinium chloride -(o-chlorobenzamido)-2-methylpyridinium chloride -(m-chlorobenzamido)p ridinium chloride -(rn-chlorobenzamido)- -methylpyridinium chloride -(m-chlorobenzamido-3-methylpyridinium chloride -(m-chlorobenzamido)-4-methylpyridinium chloride -(p-chlorobenzamido)-3-methylpyridinium chloride -(p-chlorobenzamido)-2-ethylpyridinium chloride -(p-chlorobenzamido)'2,4dimethylpyridinium chloride -(p-chlorobenzamido)-3,S-dimethylpyridinium chloride -(p-chlorobenzamido)-2,6-dimethylpyridinium chloride (p-chlorobenzamido)-5-ethyl-2-methylpyridinium chloride (p-bromobenzamido)pyridinium chloride (p-iodobenzamido)pyridinium chloride (m-anisamido)pyridinium chloride (m-anisamido)-4-metl1ylpyridinium chloride (3,4-dimethylbenzamido)pyridinium chloride (3,4-dimethylbenzamido)-3-methylpyridinium chloride 3,4-dichlorobenzamido)-2,6-dimethylpyridirlium chloride 3-chloro-p-toluamido)pyridinium chloride (3-chloro-p-toluamido)Q-methylpyridinium chloride (3-chloro-p-toluamido)-4methylpyridiniurn chloride (4-chloro-m-toluamido)pyridinium chloride (4-chloro-m-toluamido)-2-methylpyridinium chloride l-(4-chloro m-toluamido)-4methylpyridinium chloride l-( 3 ,o-dichloro-o-anisamido )pyridinium -dichloro-o-anisamido )pyridinium chloride 1-( 4-nitro-m-toluamido)pyridinium chloride l-(4-nitrom-toluamido)-3-methylpyridinium chloride l-(4-chloro-3-nitrobenzamido)-3-methylpyridinium chloride 1-(3-(methoxycarbonyl)propionamido)pyridinium chloride 1-(cyclohexylcarboxamido)pyridinium chloride 1-( l-naphthamido)pyridinium chloride l-(2-naphthamido)pyridinium chloride l-(2-furamido)pyridinium chloride l-nicotinamido-3-methylpyridinium chloride, hydrochloride l-nicotinamido-4-methylpyridinium chloride, hydrochloride 1-(Z-phenylacetamido)pyridinium chloride l-(Z-phenylacetamido)-4-methylpyridiniurr1 chloride 1-(2-(p-chlorophenyl)acetamido )pyridinium chloride l-( Z-(p-chlorophenyl)acetamido )-4-methylpyridinium chloride l-cinnamamidopyridinium chloride l-cinnamamido-4-methylpyridinium chloride l-(p-chlorocinnamamido)pyridinium chloride l-(p-chlorocinnamamido)-2-methylpyridinium chloride 1(pchlorocinnamamido )-4-methylpyridinium chloride -(2-(p-chlorophenoxy)acetamido)pyridinium chloride 1 l l l l l l l l l l l 1 1 1 l l l 1 l l 1 1 l 1 l 1 l l 1 2-(p-chlorophenoxy)acetamido)-4-methylpyridinium chloride l-(2-(4-chloro-o-tolyloxy)acetamido)pyridinium chloride l-(propoxycarbonylamino)pyridinium chloride l-(butoxycarbonylamino)pyridinium chloride l-(isobutoxycarbonylamino)pyridinium chloride l-(pentyloxycarbonylamino)pyridinium chloride l(octyloxycarbonylamino)pyridinium chloride l (phenoxycarbonylamino)pyridinium chloride l-(o-chlorophenoxycarbonylamino)pyridinium chloride 1-(pchlorophenoxycarbonylamino)pyridinium chloride l-(p-tolyloxycarbonylamino)pyridinium chloride l-(4chlor0-m-tolyloxycarbonylamino)pyridinium chloride 1-( 2,4,6-trichlorophenoxycarbonylamino)pyridinium chloride l(4-benzofuranyloxycarbonylamino)pyridinium chloride l-(B-methylureido)pyridinium chloride l-(3-phenylureido pyridinium chloride l-(3-(p-chlorophenyl)ureido)pyridinium chloride 1 (3-(m-tolyl)ureidoJpyridinium chloride 1 (3-(m-methoxypherlyl)ureido)pyridinium chloride 1 (3-(m-chlorophenyl)ureido)pyrldinium chloride l-(2,-dimethoxyphenyl)ureido)pyridinium chloride 214-6C l9l-3C 224C 2226C 23540C l88l90C 244-SOC 260-3C 246-8C 240-3C 24555C 2245C 2335C 2324C 2234C 189l91C l94l96C 2057C Continued 1-(3-(3-chlorop-tolyl)ureido)pyridinium chloride 1-(3-(4-chloro-o-tolyl)ureido)pyridinium chloride l-(3(3,4-dichlorophenyl)urcido)pyridinium chloride l-(3,3-dimethylureido)pyridinium chloride EXAMPLE 96 m.p. 176-8C m.p. l92-4C m.p. 188-190C m.p. 140C Found: C. 61.65; H. 3.80: N. 12.30711 C.61.94; H 3.91); N, 1204% yield), melting point 180C.

Analysis:

C H ClN o requires:

EXAMPLES 97-175 10 The following were prepared by analogous methods to that of Example 96:

l l l l l l l l l l 1 l l 1 1 1 1 l 1 l l 1 1 l l l 1 l 1 '1-(4-nitro-m-toluamido)pydridinium internal salt 1 1 1 1 1 l l 1 1 1 1 1 1 l I 1 1 1 1 1 1 1 l l 1 (p-Flurobenzamido)pyridinium internal salt (p-Toluamido)pyridinium internal salt (2,4-Dichlorobenzamido)pyridinium internal salt (p-Nitrobenzamido)pyridinium internal salt (3,4-dichlorobenzamido)pyridinium internal salt (p-anisamido)pyridinium internal salt (p-chlorobenzamido )-2 methylpyridinium internal salt (o-chlorobenzamido)pyridinium internal salt (o-iodobenzamido)pyridinium internal salt -(3,4-dichlorobenzamido)-2-methylpyridinium internal salt -(p-toluamido)-2-methylpyridinium internal salt -(o-toluamido)pyridinium internal salt -(o-toluamido)-4-methylpyridinium internal salt -(p-tert-butylbenzamido)-4-methylpyridinium internal salt -(o-chlorobenzamido)-2methylpyridinium internal salt -(m-chlorobenzamido)pyridinium internal salt -(mchlorobenzamido)-2-methylpyridinium internal salt -(m-chlorobenzamiclo)-3-methy1pyridinium internal salt -(m-chlorobenzamido)-4-methylpyridinium internal salt -(p-chlorobenzamido)-3-methylpyridinium internal salt -(p-chlorobenzamido)-4-methylpyridinium internal salt -(p-chlorobenzam1do)-2-ethylpyridiniurn internal salt -(p-chlorobenzamido)-3,5-dimethylpyridinium internal salt -(p-chlorobenzamido)-2,6-dimethylpyridinium internal salt -(p-chlorobenzamido)-5 ethyl-2-methylpyridinium internal salt -(p-bromobenzamido)pyridinium internal salt -(m-anisamido)-4-methylpyridinium internal salt -(3,4-dimethylbenzamido)pyridinium internal salt -(3,4-dichlorobenzamido)-2-methylpyridinium internal salt -(3,4dichlorobenzamido)-2,6-dimethylpyridinium internal salt -(3-chloro-p-toluamido)pyridinium internal salt -(3-chloro-p-toluamido)-2-methylpyridinium internal salt -(3-chloro-p-toluamido)-4-methy1pyridinium internal salt -(4-chloro-m-toluamido)pyridinium internal salt -(4-chloro-m-toluamido)-2-methylpyridinium internal salt -(4-chloro-m-toluamido)-4-methylpyridinium internal salt -(4-nitro-m-toluamido)-3-methylpyridinium internal salt -(4-chloro-3-nitrobenzamido)-3-methylpyridinium internal salt -(o-acetamidobenzamido)pyridinium internal salt -(cyclohexylcarboxamido)pyridinium internal salt -(cyclohexylcarboxamido)-3,S-dimethylpyridinium internal salt l-naphthamido)pyridinium internal salt -(2-naphthamido)pyridinium internal salt -(2-furamido)pyridinium internal salt -(2-thenamido)pyridinium internal salt -picolinamido-3-methylpyridinium internal salt -picolinamido-3-methylpyridinium internal salt, hydrochloride -picolinamido-4-methylpyridinium internal salt -(p-toluenesulphonamido)pydridinium internal salt -(2,4,5-trichlorobenzenesulphonamido)pyridinium internal salt -(4-chloro-3-nitrobenzenesulphonamido)pyridinium internal salt -(2-phenylacetamido)pyridinium internal salt -(2-phenylacetamidoJ-4-methylpyridinium internal salt -(2-(p-chlorophenyl)acetamido)-4-methylpyridinium internal salt -cinnamamidopyridinium internal salt -(p-chlorocinnamamido)pyridinium internal salt -(p-chlorocinnamamido)-2-methy1pyridinium internal salt -(p-chlorocinnamamido)-4-methylpyridinium internal salt -(2-chlorphenoxy)acetamido)-4-methylpyridinum intenral salt -(propoxycarbonylamino)pyridinium internal salt -(butoxycarbonylamino)pyridinium internal salt -(isobutoxycarbonylamino)pyridinium internal salt l-(pentyloxycarbonylamino)pyridinium internal salt l-(octyloxycarbonylamino)pyridinium internal salt l-(phenoxycarbonylamino)pyridinium internal salt l-(p-chlorophenoxycarbonylamino)pyridinium intertnal salt 1(4-chloro-m-tolyloxycarbonylamino)pyridinium internal salt mp, 202C m.p. 162C m.p. 140C mp 253C m.p. 155C m.p, 178C m.p. 145C m.p. 123C m.p. 100C m.p. 129C mp 169C mp. 125C m.pv l Ill-4C m.p. 123-5C m.p. 2002C m.p. 141C m.p. 12l-3C mpv 74C m.p. ll25C m.p. l69-l7lC m.p. 149-152C m.p. 160C liquid m.p. 50-52C m.p. 94C m.p. 6568C m.p. 186-8C m.p. -100C m.pt 150-4C m.p. 169C m.p. 3C m.p. 159-160C mp 128130C m.p. 194-6C m.p. 149-150c m.p. 1056C m.p. l58l60C m.p. 154-6C m.p. 163-4C m.p. l56-8C mp. 155-160C mp. 129-130C m.p. l4l3C m.p. ISO-2C m.p. 148-150C m.pt 2247C m.p. 2102C m.p. l8l-3C mp. 180-5C m.p. 208-210C mp. 214-6C m.p. 264-5C m.p. l95-200C mp, 70-74c m.p. 9697C mp. 129-130C m.p. 160-2C m.p. C m.p. l36l4lC m.p 2167C m.p. 6C liquid m.p. 47-49C m.p. 41-43C liquid m.p. 39-40C m.p. 116-9C m.pt 142-3C m.p. ISO-3C Continued EXAMPLES 176-204 Aqueous solutions containing 1000, 300, 100 and 30 parts per million of the compounds lifted below together with 500 ppm of a nonylphenyl/ethylene oxide condensate as wetting agent were applied to 25 mm diameter leaf discs cut from French beans, Phaseolus vulgaris, infested with 50 and 100 one day old summer eggs of the greenhouse red spider mite, Telranychus te-- Iarius. The leaf discs were then kept for 7 days at 25C on moist filter paper and the eggs examined. The proportion hatching out, by comparison with control leaf discs treated with water and wetting agent alone is tabulated below.

chlorophenyl)-2,2,2-trichloroethanol), Dimethoate O (0,0-dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate and Phenkapton (S-(2,5-dichlorophenylthiomethyl) 0,0-diethyl phosphorodithioate.) None of these acaricides was active at 100 ppm, but 1- (p-chlorobenzamido)-pyridinium chloride prevented egg hatching at 30 ppm.

EXAMPLES 206-263 Aqueous solutions or suspensions containing 1000,

20 300, 100 and 30 ppm of the compounds listed in the table below were sprayed on to the foliage of French bean plants, Phaseolus vulgaris. When the plants were Compound 1000 ppm 300 ppm 100 ppm 30 ppm l-(p-chlorobenzamido)pyridinium chloride 0 0 0 l-(p-toluamido)pyridinium chloride 0 0 0 30 l-(2,4-dichlorobenzamido)pyridinium chloride 0 0 0 60 l-(m-nitrobenzamido)pyridinium chloride 0 0 l-(p-chlorobenzamido)pyridinium internal salt 0 0 0 O l-(p-fluorobenzamido)pyridinium internal salt 0 0 l-(p-toluamido)pyridinium internal salt 0 0 l-(2,4-dichlorobenzamido)pyridinium internal salt 0 0 1-(p-toluamido)4-methylpyridinium chloride 0 0 50 80 l-(p-chlorobenzamido)2-methylpyridinium chloride 0 40 70 l(p-chlorobenzamido)-4-rnethylpyridinium chloride 0 0 0 O 1-(p-bromobenzamido)pyridinium chloride 0 0 0 0 1-(p-bromobenzamido)pyridinium internal salt 0 0 0 4O 1(p-iodobenzamido chloride 0 0 6O l-(2,4-dichlorobenzamido)pyridinium chloride 0 O 70 l-(3,4-dichlorobenzamido)pyridinium chloride 0 0 0 0 l-(3,4-dichlorobenzamido-2-methylpyridinium chloride 0 O 0 l0 1-(3,4-dichlorobenzamido)pyridinium internal salt 0 0 60 l-(3,4-dichlorobenzamido)-2-methylpyridiniurn internal salt 0 10 70 1-(4-chloro-m-to1uamido)pyridnium chlorode 0 0 60 l-( -chloro-m-toluamido)pyridinium internal salt 0 0 0 0 l-cinnamamidopyridinium internal salt 0 3O 70 l-(p-chlorocinnamamido)pyridinium chloride 0 30 6O 1-(p-chlorocinnamamido)pyridinium internal salt 0 80 l-(3,3-dimethylureido)pyridinium chloride 10 70 90 I-(p-chlorophenoxycarbonylamino)pyridinium chloride 0 1O 60 l-(p-chlorophenoxycarbonylamino)pyridinium internal salt 0 2O 70 l(4-chloro-m-tolyloxycarbonylamino)pyridinium chloride 0 0 4O 7O 1-(4-chloro-m-tolyloxycarbonylamino)pyridinium internal salt 0 0 0 60 EXAMPLE 205 A similar experiment was performed to that described in Examples 176-204 with a strain of the hop red spider mite, Tetranchus urticae, which was resistant to the comon acaricides, for example Chlorobenzilate (ethyl 4,4'-dichlorobenzilate), Chloropropylate (isopropyl 4,4'-dichlorobenzilate), Dicofol (l,l-bis(p- Compound 1000 ppm 300 ppm 100 ppm 30 ppm l-( chlorobenzamido)pyridinium chloride 0 0 0 0 l-( enzamido-2-methylpyridinium chloride 0 0 l-(p-toluamido)pyridinium chloride 0 0 0 60 l-(p-toluamido)pyridinium internal salt 0 0 O 50 l-(p-fluorobenzamido)pyridinium chloride 0 O 0 50 l-(p-fluorobenzamido)pyridinium internal salt 0 0 0 6O l-(o-chlorobenzamido)-2-methylpyridinium chloride 0 0 5O 80 1-(m-chlorobenzamido)pyridinium chloride 0 0 0 l0 l-(m-chlorobenzamido)pyridinium internal salt 0 0 O 50 l-(m-chlorobenzamido)-2-methylpyridinium chloride 0 40 l-(m-chlorobenzamido)2-methylpyridinium internal salt Continued Compound 1000 ppm 300 ppm 100 ppm 30 ppm -(p-chlorobenzamido)-2-methylpyridinium chloride 0 O O -(p-chlorobenzamido)-3-methylpyridinium chloride 0 0 0 0 -(p-chlorobenzamido)-4-methylpyridinium chloride 0 0 0 0 -(p-chlorobenzamido)-2-ethylpyridinium chloride 0 5O 9O l-(p-chlorobenzamido)pyridinium internal salt 0 0 0 0 l-(pchlorobenzamido)-2-methylpyridinium internal salt 0 0 0 0 l-(p-chlorobenzamido)-2-methylpyridinium internal salt 0 0 0 0 l-(p-chloroben2amido)-4 methylpyridinium internal salt 0 0 O 0 l-(p-chlorobenzamido)-2-ethylpyridinium internal salt 0 0 60 1-(p-chl0robenzamido)-3,S-dimethylpyridinium internal salt 0 0 O 50 l-(p-bromobenzamido)pyridinium chloride 0 0 0 O l-(p-bromobenzamido)pyridinium internal salt 0 0 0 0 l-(p-iodobenzamido)pyridinium chloride 0 0 0 0 l-( p-anisamido)pyridinium chloride 0 6O l-(p-anisamido)pyridinium internal salt 0 6O 1-(2,4-dichlorobenzamido)pyridinium chloride 0 IO 60 l-(3,4-dichlorobenzamido)pyridinium chloride 0 0 O 0 l'(3,4-dichlorobenzamido)-2-methylpyridinium chloride 0 0 0 50 l-(3,4-dichlorobenzamido)pyridinium internal salt 0 0 1O 50 l-(3,4-dichlorobenzamido)-2-methylpyridinium internal salt 0 O 50 90 l-(3,4-dichloro-N-methylbenzamido)pyridinium methyl sulphate 0 0 0 O l-(m-nitrobenzamido)pyridinium chloride 0 10 60 l-(p'nitrobenzamido)-2-methylpyridinium chloride 0 O 10 60 l-(p-nitrobenzamido)pyridinium internal salt 0 0 0 0 l(bis(p-chlorobenzoyl)amino)pyridinium chloride 0 0 0 0 l-(cyclohexylcarboxamido)pyridinium chloride 0 10 60 l-(cyclohexylcarboxamido)pyridinium internal salt 0 50 70 l-picolinamido-3-methylpyridinium internal salt 40 l-picolinamido-4-methylpyrldinium internal salt 1-(2-phenylacetamido)pyridinium chloride 40 l-cinnamamidopyridinium chloride 0 0 10 50 l-cinnamamidopyridinium internal salt 0 0 20 l-(2-(p-chlorophenoxy)acetamidopyridinium chloride 10 60 l-(butoxycarbonylamino)pyridinium chloride 0 0 20 6O l-(butoxycarbonylamino)pyridinium internal salt 0 1-(isobutoxycarbonylamino)pyridinium internal salt 0 l-(pentyloxycarbonylamino)pyridinium internal salt 0 l-(phenoxycarbonylamino)pyridinium chloride 0 0 5O l-(phenoxycarbonylamino)pyridinium internal salt 0 0 10 60 1-(p-chlorophenoxycarbonylamino)pyridinium chloride 0 0 0 0 1-(p-chlorophenoxycarbonylamrno)pyndrnrum mtemal salt 0 0 0 Q l-(p-tolyloxycarbonylamino)pyridinium chloride 0 0 0 l (4-chloro-m-tolyloxycarbonylamino)pyridinium internal salt 0 0 O l-(4-benzofuranyloxycarbonylamino)pyridinium chloride 0 0 0 l-(4-benzofuranyloxycarbonylamino)pyridinium internal salt 0 20 80 3-p-chlorophenyl)ureido)pyridinium chloride EXAMPLE 264 French bean plants, Phaseolus vulgaris, were grown in mm diameter pots and the soil watered with 10 ml of a 1000 ppm aqueous solution of l-(pchlorobenzamido)pyridinium chloride. After 24 hours the plants were infested with adult female red spider mites, Tetranychus telarius, which were allowed to feed on the foliage for 24 hours and then removed to untreated plants. None of the eggs which they laid during the next 48 hours hatched out, demonstrating the systemic activity of the compound.

EXAMPLE 265 Aqueous solutions containing 1000 and 300 parts per million of l-(p-chlorobenzamido)-2-methylpyridinium chloride were sprayed on to young french bean plants, Phaseolus vulgaris which had previously been infested with 50 adult greenhouse red spider mites Tetranychus telarius. The treated plants were then kept at 25C for 48 hours, after which time all the mites were found to be dead.

EXAMPLE 266 l-(3,4-dichlorobenzamido)pyridinium internal salt (20 parts) and dimethyl sulphate parts) were heated together at 100C for 4 hours. On cooling, crystals separated which were filtered off, washed and dried to give l-(3,4-dichloro-N-methylbenzamido) pyridinium methyl sulphate (15 parts), melting point C.

EXAMPLE 267 A solution of l-(p-chlorobenzamido)pyridinium internal salt (20 parts) in p-chlorobenzoyl chloride was allowed to stand for 2 hours at 25C. The crystalline solid which formed was filtered off, washed and dried to give l-(bis(p-chlorobenzoyl) amino)pyridinium chloride (20 parts), melting point C. Analysis:

Found C, 55.65; H, C, H,;,Cl N- O requires: C, 55.97; H,

EXAMPLE 268 A suitable wettable powder formulation was prepared by admixing:

l-(p-chlorobenmmido)pyridinium internal salt Wetting agent Dyapol PFS (sodium salt of sulphonated cresol/formaldehyde condensate), defloculating 25% by weight 3% by weight 3% by weight 17 in which R, R R, R and R are the same or different and each represents hydrogen or alkyl of l to 4 carbon atoms;

R represents a group of formula COR" in which R represents phenyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, nitro and alkoxy of l to 4 carbon atoms; phenylalkyl of 7 to 10 carbon atoms; phenylalkyl of 7 to 10 carbon atoms substituted by halogen; cycloalkyl of 3 to 8 carbon atoms;

R represents hydrogen, alkyl of 1 to 4 carbon atoms or benzoyl substituted by halogen; and

X represents one equivalent of an acaracidally effective anion.

2. A compound according to claim 1 wherein R represents phenyl substituted by one or more groups selected from halogen, alkyl of l to 4 carbon atoms, nitro and alkoxy of l to 4 carbon atoms; phenylalkyl of 7 to 10 carbon atoms; cycloalkyl of 3 to 8 carbon atoms.

3. A compound according to claim 1 wherein R represents hydrogen.

4. A compound according to claim 1 wherein at least three of R, R R, R and R represents hydrogen.

5. A compound according to claim 1 wherein at least four of R, R R, R and R represents hydrogen.

6. A compound according to claim 1 wherein at least one of R and R represents hydrogen.

7. A compound of general formula 4 carbon atoms; R represents benzoyl substituted by one or two substituents selected from halogen, alkyl of l to 4 carbon atoms and nitro; and X represents one equivalent of an acaracidally effective anion.

8. A compound according to claim 7 wherein X represents chloride.

9. A compound according to claim 7 which is a l-(p chlorobenzamido) pyridinium salt.

10. A compound according to claim 7 which is a l- (p-chlorobenzamido)-2-methylpyridinium salt.

11. A compound according to claim 7 which is a l- (p-chlorobenzamido)-3-methylpyridinium salt.

12. A compound according to claim 7 which is a l- (p-chlorobenzamido)-4-methylpyridinium salt.

13. A compound according to claim 7 which is a l- (3,4-dichlorobenzamido)pyridinium salt.

14. A compound according to claim 7 which is a l- (4-nitrobenzamido)pyridinium salt.

15. A compound according to claim 9 which is the internal salt.

16. A compound according to claim 9 which is the chloride.

17. A compound according to claim 7 wherein R, R R, R and R are each hydrogen.

18. A compound according to claim 7 wherein R represents benzoyl substituted by one or two halogens.

19. A compound according to claim 18 wherein the halogens are chlorine.

Patent No.

May 27,1975

3 ,886 ,171 Dated Inventor(s) John Henry PARSONS It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, between the formula (I) and (II) insert X or Claim 1, between the formula (I) and (II) insert X or Claim 7 between the formula (I) and (II) insert X" or M in formula (I) change "R to Signed and Scaled this Thirty-first Day of August 1976 Arrest:

RUTH C. MASON Arresting Officer 

1. A COMPOUND OF GENERAL FORMULA
 2. A compound according to claim 1 wherein R10 represents phenyl substituted by one or more groups selected from halogen, alkyl of 1 to 4 carbon atoms, nitro and alkoxy of 1 to 4 carbon atoms; phenylalkyl of 7 to 10 carbon atoms; cycloalkyl of 3 to 8 carbon atoms.
 3. A compound according to claim 1 wherein R7 represents hydrogen.
 4. A compound according to claim 1 wherein at least three of R1, R2, R3, R4 and R5 represents hydrogen.
 5. A compound according to claim 1 wherein at least four of R1, R2, R3, R4 and R5 represents hydrogen.
 6. A compound according to claim 1 wherein at least one of R1 and R5 represents hydrogen.
 7. A compound of general formula
 8. A compound according to claim 7 wherein X represents chloride.
 9. A compound according to claim 7 which is a 1-(p-chlorobenzamido) pyridinium salt.
 10. A compound according to claim 7 which is a 1-(p-chlorobenzamido)-2-methylpyridinium salt.
 11. A compound according to claim 7 which is a 1-(p-chlorobenzamido)-3-methylpyridinium salt.
 12. A compound according to claim 7 which is a 1-(p-chlorobenzamido)-4-methylpyridinium salt.
 13. A compound according to claim 7 which is a 1-(3,4-dichlorobenzamido)pyridinium salt.
 14. A compound according to claim 7 which is a 1-(4-nitrobenzamido)pyridinium salt.
 15. A compound according to claim 9 which is the internal salt.
 16. A compound according to claim 9 which is the chloride.
 17. A compound according to claim 7 wherein R1, R2, R3, R4 and R5 are each hydrogen.
 18. A compound according to claim 7 wherein R6 represents benzoyl substituted by one or two halogens.
 19. A compound according to claim 18 wherein the halogens are chlorine. 